Processes for obtaining a polyol from palm oil, polyols obtained from said processes, products derived from said polyol and method for preparing same

ABSTRACT

The present invention relates to the process for production of a polyol from palm oil and of rigid polyurethane foams prepared from said polyol derived from palm oil. On the one hand, this invention provides a method for obtaining monomeric polyols from palm oil that have hydroxyl number between 50 450 mgKOH/g sample. The polyols of the present application may be obtained by means of a procedure based on the following four mother routes: Route 1: maleinisation of the fatty acids of palm oil; Route 2: glycerolysis of palm oil; Route 3: trancesterification of palm oil; and Route 4: epoxidation of unsaturated carbon-carbon links of palm oil. Additionally, other modalities of the invention permit obtaining polyols from the combination of these mother routes. In other realizations of the invention polyurethanes are prepared from polyols obtained through any of the four routes or by combinations of the same. In a mode of the invention the polyurethanes are produced through the reaction of a mixture of a polyol obtained through the present invention, a commercial polyol, a surfactant, a catalyst and an isocyanate. The polyurethanes may be foams of rigid high density polyurethane.

FIELD OF THE INVENTION

Synthetic polymers were invented about 60 years ago and from then onmuch progress has been achieved in the field of their applications.Polyurethane is a polymer obtained through condensation of polyolscombined with polyisocyanates. It is subdivided in two major groups:thermostables and thermoplastics. The more usual thermostablepolyurethanes are foams frequently used as thermal insulators and asresilient foams, but there are also polyurethanes that are highperformance elastomers, adhesives and sealants, paints, fibers,packaging sealants, joints, preservatives, automobile components,elements in the construction industry, furniture industry, and othermultiple applications.

Polyols used in the production of polyurethanes are generally compoundswith molecular weight in the range of 500 to 5000 g/mol. Depending ofthe length of the chain of these diols and glycols, the properties ofthe polyurethanes change. If the polyol has a low molecular weight, itmakes rigid plastics, and if it has a high molecular weight it producesflexible elastomers. Polyols are reactive substances, usually liquids,which contain at least two groups that react to isocyanate linked to onemolecule. They have a deep effect in the properties of finishedpolyurethane. The properties of the polymers are associated with thelinks to isocyanate, but the structure of polyol exercises a directaction on the processing and finishing properties of the polymer.

BACKGROUND OF THE INVENTION

The polyols used in the polyurethane production industry are generallyderived from petroleum, but currently there is a trend to use renewablesources such as vegetable oils for production of polyols based on theseoils.

The production of polyols from of vegetable oils has been described inseveral documents in the state of the art:

Patent Application U.S. 20070232816 reveals a process for the productionof a polyol monomer which consists of reacting an unsaturated acid fattyor its corresponding triglycerides with a polyhydric alcohol in thepresence of a catalyst and an emulsifier in order to prepare amonoglyceride. Said process also comprises an epoxidation stage of theunsaturated fatty acids of said monoglyceride, and a reaction stage ofthe epoxidized monoglyceride with a polyhydric alcohol.

Publication W0/2006/012344 provides methods for the preparation ofunsaturated polyols based one modified vegetable oils, as well asmethods for the production of oligomeric polyols based on modifiedvegetable oils. This publication shows a method of manufacturing anoligomeric polyol based on a modified vegetable oil, where a mixture ismade to react that comprises an epoxidized oil vegetable and a compoundthat allows the opening of the ring for form an oligomeric polyol basedon the modified vegetable oil, where the oligomeric polyol based on themodified vegetable oil comprises at least 20% of oligomers and has aviscosity at 25° C. less than approximately 8 Pa s.

Publication W0/2009/058367, as well as Publication W0/2009/058368 referto methods for obtaining a polyester polyol from natural oils. Suchmethods comprise the stage of reacting the monohydric fatty acids to theesters with a multifunctional reagent initiator to form the polyesterpolyol. This document reveals a process where a methanolysis of oils(Sunflower, Soya, Canola) is performed followed by an epoxidationprocess.

U.S. Pat. No. 6,433,121 reveals a method for the production of polyolsbased on natural oils through the use of a two consecutive-stage processinvolving epoxidation and hydroxylation. This document mentions in ageneral manner that palm oil may be used; however, without limitation,the preferred realization of the invention corresponds to the use ofsoybean oil.

Publication W0/2009/058368 reveals methods for the obtaining a polyesterpolyol from natural oils. Said method comprises a stage of reacting thehydroxylated fatty acids to the esters with a reagent multifunctionalinitiator to form polyester polyol. The process revealed in thisdocument performs a methanolysis of oils (Sunflower, Soya, Canola)followed by a process of epoxidation. Additionally, the documentmentions in a general way that palm oil could be employed in theprocess.

In the research published in the Article by G. Ruiz Aviles, “Obtainingand characterizing of a biodegradable polymer from Cassava starch,”Engineering and Science, Medellin, 2006, a biodegradable polymer isobtained from yucca starch by processing modified starch mixtures withglycerin and water as plasticizers, using an open mill and a singleextruder spindle. The variables to control during the extrusion are:temperature, torque and spindle rotation speed profile. The polymerobtained has applications in food packaging and for garbage bags.

On the other hand, the article by H. Yeganeh, P. et al., “Preparationand properties of novel biodegradable polyurethane networks based oncastor oil and poly(ethylene glycol),” Polymer Degradation and Stability92, Iran, 2007, reveals a method of preparation of polyurethane withpolyols obtained from castor oil and mixtures with polyethylene glycolthat were synthesized through the reaction of the prepolymer with 1,6hexamethylene diisocyanate. The polymer obtained has a rate ofbiodegradability compatible for be used in biomedical applications.

The article by S. Ahmad, Md, et al., “Urethane modified boron filledpolyesteramide: a novel anti-microbial polymer from a sustainableresource,” European Polymer Journal, 2004 describes a procedure forobtaining an antimicrobial polymer from soybean oil; the polymer iscomposed of polyesteramide filled with boron that is polymerized forform a polyester amide urethane. The material obtained was evaluated forantimicrobial and antifungal activity, verifying that the differentcompositions inhibit microbial growth.

Another article, by V. Sharma, et al., “Addition polymers from naturaloils: A review,” Prog Polym. Sci. 31, India, summarizes the theoreticalaspects of the production of polymers from renewable sources, especiallyfrom vegetable oils, showing the differences in the structure of eachoil and its influence on the polymer properties. It poses variousalternatives for natural oils such as soy, corn, tung, linseed, castoroil plant and fish oil for the production of polymer materials.

Finally, the article by G. Gunduzb, et al., “Water-borne and air-dryingoil-based resins,” Progress in Organic Coatings 49, Turkey 2003,presents a procedure for the preparation of polyurethane dispersed inwater for application as a varnish. The resin is produced for thepreparing a maleinised monoglyceride, TDI as isocyanate, silicone, andethylene diamine. Sunflower oil was used for this development as arenewable resource to produce the monoglycerides.

Palm oil is the second most cultivated vegetable oil in the worldfollowing soybean oil. Ninety percent of palm oil produced is exportedfrom Malaysia and Indonesia. Palm oil is derived from the fruitsclusters of the palm, is semisolid at environmental temperature due tothe combination of triglycerides of high and low fusion points, and hasa red-orange color due to its high content of carotenes. It is composedmainly of fatty acids, the amounts typical of these acids being: 45%palmitic, 40% oleic, 10% linoleic and 5% stearic. Thanks to its goodresistance to oxidation and to heating at high temperatures, palm oil isemployed in diverse industries for its good performance and economy. Inenergetic terms palm oil requires less energy than others oils for theproduction of one ton, such as soy and rapeseed oils.

Initially palm oil production was only used for human consumption, butin view of the overproduction of palm oil of in Malaysia, Thailand andIndonesia, the need to search for alternative uses for the oil has beenidentified. Some different areas of knowledge have been identified forits use, such as medicine, agriculture development of new materials,civil works, and biofuels, among others.

The production of polyols to from of palm oil, specifically oligomericpolyols, has been described in Publication W0/2007/123637, whichdiscloses oligomeric polyols obtained from palm oil and compositionsthat comprise these polyols, as well as a process for obtaining anoligomeric polyol based on modified palm oil, which comprises providingan epoxidized composition based on palm oil and making it react with acompound that allows the opening of the ring to form an oligomericpolyol where the oligomeric polyol based on the modified palm oilcomprises at least 40% oligomers by weight, has a hydroxyl number ofaround of 65 mg KOH/g sample or less, an average number of hydroxylfunctionality of 2.5 or less, and viscosity at 25° C. of less thanapproximately 4 Pa s.

While the prior art has searched for solutions to the technical problem,which is to provide methods for obtaining “green” polyols, that is, fromvegetable oils which include palm oil, as well as obtaining polyurethanefoams from of these “green” polyols with properties that allow theirapplication in the different uses mentioned above, none of the documentsof the prior art refers to a procedure for obtaining polyols derivedfrom palm for the preparation of polyurethane, in which two methods ofpreparation are combined to grant a higher functional ty to the finalmolecular structure. This improves the characteristics of thepolyurethane obtained from said polyol, conferring properties such asgreater functionality and greater crosslinking.

Although in other inventions polyols have been obtained from vegetableoils, the products prepared from such polyols are brittle due to theconcentration of hydroxyl groups at only one end of the carbon chain.

Additionally and in relation to the conditions of operation of theglycerolysis method, the present invention achieved decreasing thereaction temperature for obtaining a polyol with favorable resultsregarding the decrease in energy costs.

The present invention provides a simple method for its realization, isnot expensive, and gives the end result of a product with high technicaland functional qualities that places it above those of conventional typeand within the same line found in the prior art, with the advantage ofhaving in its raw materials a polyol from renewable natural sources.

The present invention produces polyols with molecular weights between314 and 3366 and with a hydroxyl number of between 50 and 450 mg KOH/gsample.

The resulting rigid foams were tested for the density (according to STMC373-88) with results between 0.284 and 0.658 g/cm³, Young module(according to ASTM 0695-10) with results between 8.94522 and 54.92330MPa, and maximum effort (according to ASTM 0695-10) with results between0.92037 and 8.29101 MPa.

The resulting semi-rigid foams were tested for density (according toASTM C373-88) with results between 0.129 and 0.158 g/cm3, Young module(according to ASTM 0695-10) with results between 0.78727 and 1.54311MPa, and maximum effort (according to ASTM 0695-10) with results between0.07012 and 0.09753 MPa.

DESCRIPTION OF THE INVENTION

The present invention is related to the production process of a polyolfrom palm oil and to rigid polyurethane foams prepared from said polyolderived from palm oil.

On the one hand, the present invention provides a method for obtainingmonomeric polyols from palm oil that have a hydroxyl number of between50 450 mgKOH/g sample.

The polyols of the present application may be obtained by means of aprocedure based on the following four mother routes:

-   -   Route 1: maleinization of the fatty acids of palm oil    -   Route 2: glycerolysis of palm oil    -   Route 3: transesterification of palm oil    -   Route 4: epoxidation of unsaturated carbon-carbon bonds in palm        oil

Additionally, other modalities of the invention allow the obtainingpolyol from the combination of these mother routes.

Specifically, route 1 begins with the alcoholysis of palm oil to obtainfatty acids, which undergo a maleinization process in order to introducecarboxylic groups and from these to extend the glycerin chain and soobtain a polyol from palm oil.

In the mother route 2 of the present invention monoglycerides areprepared from the palm oil but, in contrast to route 1, no maleinizationis performed. Rather, polyol is obtained from the palm oil by means ofglycerolysis process. The glycerolysis takes place at temperaturesbetween 170 and 280° C., obtaining higher reaction speeds the higher thetemperature. It is recommended not to exceed 260° C. in any case,provide a good system of agitation (350 to 420 rpm) and use an inertatmosphere (Nitrogen, argon or CO2).

The process of glycerolysis is usually performed in presence of asolvent and a catalyst. The selection of a good catalyst allows usinglower temperatures.

The glycerolysis reaction should be carried out under the action of acatalyst that can be homogeneous (acid or base) or heterogeneous.Examples of the catalysts to obtain mono and di glycerides include leadacetate, calcium acetate, lead oxide and lithium ricinoleate, sulfuricacid, hydrochloric acid, sulfonic acid and sodium hydroxide.

Lead and calcium acetates, as well as the lithium ricinoleate, allowobtaining an excellent glycerolysis in the minimum time (40 to 50minutes) and relatively moderate temperature (235 to 240° C.) and, moreimportantly, using minimum amounts of catalyst.

The mother route 3 of the present invention corresponds to thepreparation of a polyol from palm oil modified throughtransesterification with pentaerythritol, which is useful when aconsiderable increase in tensile, hardness and resistance to chemicalattack properties is required. This is due to a higher degree ofcrosslinking caused by the increase in the content of hydroxyl groups.

In mother route 4 of the present invention a polyol to from palm oil isproduced by double link epoxidation, in which a process of methanolysisof the palm oil is initially performed to obtain of fatty acid methylesters (FAME), which are submitted to a process of epoxidation withhydrogen peroxide to generate performic acid in situ.

In other aspect of the invention polyurethanes are prepared from thepolyols obtained through any of the four routes or through a combinationof the same. In a modality of the invention, the polyurethanes areproduced through the reaction of a mixture of polyol obtained throughthe present invention, a commercial polyol, a surfactant, a catalyst andan isocyanate. The polyurethanes may be foams of high density rigidpolyurethane.

The specific characteristics, advantages and novel characteristics ofthis invention will be established in the following section of thedescription, corresponding to the detailed description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a flow chart exemplifying the production of a polyol frompalm oil through Route 1.

FIG. 2 shows a flow chart exemplifying the production of a polyol frompalm oil through Route 2.

FIG. 3 shows a flow chart exemplifying the production of a polyol frompalm oil through Route 3.

FIG. 4 shows a flow chart exemplifying the production of a polyol frompalm oil through Route 4.

FIG. 5 shows a flow chart exemplifying the production of a polyol frompalm oil through the combination of Route 4 and Route 2.

DETAILED DESCRIPTION THE INVENTION

The present invention relates to a process for the production of apolyol from palm oil and of rigid polyurethane foams with a polyolderived from palm oil mixed with a commercial polyol.

The processes for the production of the polyols based on palm oil willbe described by referring to FIGS. 1 to 5.

FIG. 1 describes route 1 in a general manner. Specifically, this routeincludes two different methods, the first comprising the maleinizationof palm oil through heating of the same and its mixture with maleicanhydride. The mixture is later reacted in the presence of refluxcondenser and an inert atmosphere, and the reaction happens there duringan established period, obtaining the polyol.

The second method corresponds to the maleinization of fatty acids,beginning with a mixture of palm oil and sodium hydroxide and anethanol-water solution. The mixture obtained is heated and stirred.Subsequently a small amount of concentrated sulfuric acid is added,showing the separation of the organic phase and the aqueous phase.

Then, saturated sodium chloride solution is added. After of the completeseparation of the phases, the aqueous phase is eliminated. By means ofwarming and agitation of the organic phase the fatty acids may beobtained, which are mixed with previously blocked glycerol through anMEK (Methyl ethyl ketone) reaction, carried out with sulfonic tolueneacid as a catalyst and toluene as a solvent. The fatty acids then reactwith the glycerol blocked in the presence of a catalyst, sulfonictoluene acid, and heat. The product of this reaction is evaporated toobtain blocked monoglyceride, which subsequently reacts in a nitrogenand maleic anhydride atmosphere. Sulfuric acid is added to the productof this reaction. The organic phase obtained is washed and submitted toevaporation to finally obtain the polyol.

Now thus, FIG. 2 summarizes route 2 which corresponds to the productionof polyol from palm oil through glycerolysis. This route comprises thereaction between the palm oil and glycerol, terbutanol as a solvent andsodium hydroxide as a catalyst in the presence of heat. The product ofthis reaction is neutralized with hydrochloric acid and submitted toevaporation for elimination of the solvent. The phase obtained isseparate through the addition of n-hexane, allowing the residualglycerin to be discarded from the polyol finely obtained.

FIG. 3 summarizes route 3, related to the production of polyol from palmoil modified through transesterification with pentaerythritol. Thisroute comprises the reaction between palm oil, pentaerythritol and leadoxide in the presence of heat with continuous agitation and in an inertnitrogen atmosphere. The product of the reaction is treated withn-hexane, allowing formation of two phases: the precipitate thatcontains glycerol is then discarded and the other phase is submitted toevaporation to obtain the polyol.

On the other hand, route 4 is summarized in FIG. 4 and comprises aprocess of epoxidation of the fatty acid methyl esters of (FAME), whichare previously obtained through methanolysis of palm oil. Thismethanolysis comprises the reaction between the palm oil and methanol inpresence of sodium hydroxide. Subsequently the glycerin phase isdiscarded and the phase of interest is washed with phosphoric acid,discarding the solids formed and neutralizing. The product (FAME) issubmitted to evaporation to remove the excess methanol.

In this way, the FAME are made to react with formic acid in the presenceof hydrogen peroxide. The reaction is evidenced by the color change fromorange to clear yellow. Subsequently, the product is washed with water,sodium bicarbonate and sodium chloride, neutralizing the solution, whichthen undergoes evaporation to remove the moisture and allow obtainingthe polyol.

FIG. 5 describes other modalities of the invention, which correspond tothe combination of routes 2 and 4 and are established in more detailbelow.

One of these modalities allows obtaining polyol from of the olein phaseof crude palm oil, using lead oxide as a catalyst. The method is thencarried out through the epoxidation of the olein phase of crude palm oilwith formic acid, in the presence of heat. Subsequently hydrogenperoxide is added and stirred. The reaction is evidenced by the changeof color from orange to clear yellow. The product of the reaction iswashed with water, sodium bicarbonate and sodium chloride, discardingthe aqueous phase and subjecting the organic phase to glycerolysis(reaction with glycerin) using lead oxide as catalyst to thus obtainedthe polyol.

Another mode of the invention corresponds to obtaining the polyol fromthe olein phase of crude palm oil using NaOH as a catalyst. This modecomprises the same steps mentioned for the previous mode, with thedifference that the glycerolysis of the organic phase is done in thepresence of sodium hydroxide, with a posterior neutralization of theexcess catalyst with phosphoric acid.

Yet another mode of the invention allows obtaining polyol from the oleinphase of refined, bleached and deodorized palm oil (RBD). For thispurpose the same steps are used as for the previous embodiments, usingthe raw material mentioned and sodium hydroxide as a catalyst in theglycerolysis.

The last mode corresponds to obtaining polyol from of the olein phase ofrefined, bleached and deodorized palm oil (RBD), but employing leadoxide as catalyst. In the same way, the steps already mentioned aboveare used, with the exception that the olein phase of RBD is used as rawmaterial and lead oxide as catalyst in the glycerolysis.

The routes and modalities described thus allow obtaining thepolyurethane foams through the reaction of the polyols produced withmethylene diphenyl diisocyanate (MDI).

For said purpose, the polyol obtained is mixted with a short chainpolyol (diethylene 1,6 butanediol), a catalyst (dibutyltin dilaurate,tin octoate, tertiary amine catalysts, water, a surfactant (Silicone ororganosiloxane-based), and methylene diphenyl diisocyanate (MDI). Thereaction leads to the formation of foam of rigid polyurethane.

Depending on the hydroxyl number obtained for the polyol, flexible,semi-rigid and rigid polyurethane foams may be obtained, as indicatedbelow:

Hydroxyl No. 50 100 150 200 250 300 350 400 Foam Type FlexibleSemi-rigid Rigid

Within of the applications that these types of foam have, the followingmay be noted:

Polyurethane Application Rigid Molded parts, soles for footwearSemi-rigid Thermal insulation, soundproofing insulation, waterproofing,floral foam, chairs adapted to the user (mainly for disabled people)Flexible Foam for bras, mattresses

EXAMPLES

The following examples is presented with the purpose of illustrating theinvention and are in no way a limitation, inasmuch as the personmoderately skilled in the matter can recognize the possible variations.

Example 1 Obtaining Polyol Using the First Method of Route 1

300 grams of palm oil were laced in the 250 ml reaction flask.Separately, 65.7 grams of maleic anhydride were weighed and were addedto the reaction flask. The same was heated to 180° C. Subsequently thereflux condenser was adapted and the reaction flask placed on a heatingiron with magnetic agitation to 1300 allowing the reaction to take placeduring 3 hours in a low nitrogen atmosphere. The product of thisreaction is the maleinised oil that was cooled to the 100° C. and towhich an amount of 30.85 g of glycerol was added. The reaction wasallowed to continue and the acidity index tracked every 30 minutes up toa value of 90 mg KOH/g sample, thus obtaining the polyol.

Example 2 Obtaining Polyol Using the Second Method of Route 2

150 grams of palm oil were placed in a 1000 ml precipitation glass.Subsequently 33.5 g of NaOH and 100 ml of a 1:1 ethanol-water solutionwere added. The reaction was carried out at a temperature of 80° C.during 30 minutes. The solution was stirred slightly in manual form.Then, drops of concentrated sulfuric acid were added. The separation ofthe organic phase and the aqueous phase was then observed. To completethe solution, 100 ml of saturated sodium chloride solution were added.The solution was left at rest while the phases separated. Subsequentlythe aqueous phase was discarded and is the rest transferred to aseparation funnel, washing with hot water. The pH of discarded washwater was measured to verify it was neutral. Separately, the organicphase was transferred to an lateral release Erlenmeyer, the temperaturewas increased to 80° C., and the phase was stirred continuously; Thisprocedure was carried out in a vacuum. The fatty acids were obtained asa product.

70.83 grams of glycerol were separately weighed and placed in a 500 mlreaction flask. Then 62.90 grams of MEK (methyl ethyl ketone) were addedtogether with 1.8 grams of sulfonic toluene acid and 70 ml of toluene.The reaction was carried out at 90° C. during 2 hours. In this way theblocked glycerol was obtained.

To 40 grams of the fatty acids obtained above, 19.5 grams of blockedglycerol were added in a 500 ml reactor. Subsequently 1.8 grams ofsulfonic toluene acid were added and the remaining solution underwentheating at 90° C. with magnetic agitation of 1200 rpm, leaving thereaction to develop for three and a half hours. Then the product of thereaction was moved to a separation funnel, also washing with hot waterand measuring the pH of outgoing wash water until it was neutral. Theproduct of this washing is consecutively put under rotoevaporationduring 3 hours at a temperature of 90° C. and in vacuum conditions. Bythese means the blocked monoglyceride was obtained. Afterwards 25 gramsof the blocked monoglyceride are taken and placed in a 500 ml reactionflask. Subsequently 9.2 grams of maleic anhydride are added and thereaction is carried out at 200° C. with magnetic agitation during 3hours in a low nitrogen atmosphere. The product is left to cool to 100°C. without stopping the agitation. Four drops of concentrated sulphuricacid are immediately added slowly, dissolved in 3 ml of distilled water,and the reaction is allowed for another hour. A hot water wash is thencarried out and the result left decanting throughout the night.

The following day is the aqueous phase was discarded and the organicphase was rotoevaporated at 80° C. during an hour and a half, thusobtaining the polyol.

Example 3 Obtaining Polyol Using Route 2

In a 500 ml reaction flask, coupled with a reflux condenser, a heatingsurface and a magnetic agitator, 64.5 grams of palm oil were added,along with 40 grams of glycerol, 20 ml of terbutanol and 4.5 grams ofsodium hydroxide. The conditions of operation were, temperature: 90° C.,time: 2 hours and agitation: 1300 rpm.

Once the time of reaction had elapsed the mixture was cooled totemperature and the catalyst neutralized with an HCl solution at 10%,verifying the pH with a paper indicator. The glycerin and the residualsolvent were then removed and the product of interest was rotoevaporatedto ensure the complete elimination of solvent in the solution. Therotoevaporation temperature was 90° C. and was carried out during 3hours.

Finally the phases were separated in a separation funnel, where 60 ml ofn-hexane were added with vigorous stirring and constant releasing ofpressure. The result was left in repose and the bottom phase discarded,which contained residual glycerin. A polyol was obtained with a hydroxylnumber value of 523.23 mg KOH/g sample.

Example 4 Obtaining Polyol Using Route 3

In a 500 ml reaction flask 40.0 grams of palm oil were weighed, alongwith 4.32 grams of pentaerythritol and 0.02 grams of lead oxide.Subsequently, the flask was placed on a heating surface where themixture remained in reaction at a temperature of 200° C., withcontinuous agitation, an inert atmosphere of nitrogen and water refluxcondenser during 2 hours. It was then left to cool and 40 ml of n-hexanewere added in a separation funnel, stirring and releasing pressure. Thephases were allowed to separate to further discard the precipitate andthe glycerol. The other phase was submitted to rotoevaporation at 70° C.with constant agitation for 3 hours, thus obtaining the polyol, with ahydroxyl number value of 11.86 mg KOH/g sample.

Example 5 Obtaining Polyol Using Route 4

Initially the methanolysis of palm oil was carried out, in a 500 mlreaction flask, taking 500 grams of palm oil, together with 160.8 g ofmethanol and 9 grams of sodium hydroxide. The mixture was carried out ata temperature of 70° C. with agitation of 1000 rpm during 1 and a halfhours.

After the reaction time, the product was taken to a separation funnel todiscard the glycerin phase that was in the bottom. The phase of interestwas then washed with 100 ml of 0,015N phosphoric acid at 60° C., thesolids formed were discarded, and repeated the wash was repeated withwater at 60° C. until the pH was neutralized. The phase of interest wasthen submitted to rotoevaporation during 3 hours at a temperature of 80°C., for removal of excess methanol. The product obtained corresponds tothe fatty acid methyl esters (FAME).

Separately, in a 1000 ml reaction flask, 190 grams of FAME were addedalong with 7.71 grams of formic acid. The mixture was heated at 40° C.and agitated at 800 rpm.

20.85 grams of hydrogen peroxide were then added drop by drop during 1hour. After the addition of hydrogen peroxide, the reaction continuedduring 11 hours with constant temperature and agitation. The evidence ofthe reaction was seen in the change of color from orange to clearyellow. Hot water washes were immediately conducted with until the pHincreased to 5. Then a washing with 100 ml of bicarbonate sodiumsolution at 5% and sodium chloride at 5% was performed. The processended with hot water washes until completely neutralized.

The resulting mixture was rotoevaporated during 4 hours at 90° C. toremove moisture. The polyol was obtained.

Example 6 Obtaining Polyol Using Routes 2 and 4 (Epoxidation andGlycerolysis) from the Olein Phase of Crude Palm Oil and Using LeadOxide as Catalyst

200 grams of the olein phase of crude palm oil and 9.97 grams of formicacid were placed in a 500 ml reaction flask, coupled with a refluxcondenser, a heating surface to achieve a temperature of 50° C., andmagnetic agitation to 800 rpm. The reaction was started and 22.11 gramsof hydrogen peroxide were added drop by drop, with agitation constantduring 90 minutes. The reaction was allowed to continue during 2 hours.The formation reaction of epoxidized oil was evidenced by a change ofcolor from orange to clear yellow.

Hot water washes were then is conducted until a pH close to 5. A washwas performed with a solution of 5% sodium bicarbonate and with a 5%sodium chloride solution. The aqueous phase was discarded through aseparation funnel of and the organic phase transferred to a lateralrelease Erlenmeyer, drying in a vacuum during 3 hours at 80° C. Theglycerolysis was then carried out with 100 grams of epoxidized oil,25.72 grams of glycerin and 0.03 grams of PbO in a 500 ml reaction flaskcoupled with a reflux condenser, temperature at 215° C., and agitationof 1300 rpm during 45 minutes. The polyol obtained was analyzed,resulting in hydroxyl numbers of between 60 and 110 mg KOH/g sample.

Example 7 Obtaining Polyol Using Routes 2 and 4 (Epoxidation andGlycerolysis) from of the Olein Phase of Crude Palm Oil and Using SodiumHydroxide as Catalyst

200 grams of the olein phase of crude palm oil and 9.97 grams of formicacid were placed in a 500 ml reaction flask coupled with a refluxcondenser, a heating surface to reach a temperature of 50° C. andmagnetic agitation to 800 rpm. The reaction was initiated and 22.11grams of hydrogen peroxide were added drop by drop, with constantagitation during 90 minutes. The reaction continued during 2 additionalhours. The reaction of formation of epoxidized oil was evidenced by achange of color from orange to clear yellow.

Hot water washes were then carried out up to a pH close to 5. A wash wasperformed with a of 5% sodium bicarbonate solution and with a 5% sodiumchloride solution. The aqueous phase was discarded through a separatingfunnel and the organic phase was transferred to a lateral releaseErlenmeyer, drying in a vacuum during 3 hours at 80° C. Subsequently theglycerolysis was performed with 100 grams of epoxidized oil, 25.72 gramsof glycerin and 1 gram of NaOH in a 500 ml reaction flask coupled with areflux condenser, temperature of 180° C. and agitation at 1300 rpm for45 minutes.

The catalyst was neutralized with drops of phosphoric acid, thusavoiding the formation of soaps. Finally, the polyol obtained wasanalyzed. It yielded hydroxyl numbers between 400 and 440 mg KOH/gsample.

Example 8 Obtaining Polyol Using Routes 2 and 4 (Epoxidation andGlycerolysis) from the Olein Phase of Refined Bleached Deodorized CrudePalm Oil and Using Sodium Hydroxide as Catalyst

200 grams of the olein phase of crude palm oil and 9.97 grams of formicacid were placed in a 500 ml reaction flask, coupled with a refluxcondenser, a heating surface to achieve a temperature of 50° C., andmagnetic agitation to 800 rpm. The reaction was initiated and 22.11grams of hydrogen peroxide were added drop by drop, with constantagitation during 90 minutes. The reaction continued during 2 additionalhours. The reaction of formation of epoxidized oil was evidenced by achange of color from orange to clear yellow.

Hot water washes were then carried out up to a pH close to 5. A wash wasperformed with a of 5% sodium bicarbonate solution and with a 5% sodiumchloride solution. The aqueous phase was discarded through a separatingfunnel and the organic phase was transferred to a lateral releaseErlenmeyer, drying in a vacuum during 3 hours at 80° C. Subsequently theglycerolysis was performed with 100 grams of epoxidized oil, 25.72 gramsof glycerin and 1 gram of NaOH in a 500 ml reaction flask coupled with areflux condenser, temperature of 180° C. and agitation at 1300 rpm for45 minutes.

The catalyst was neutralized with drops of phosphoric acid, thusavoiding the formation of soaps. Finally, the polyol obtained wasanalyzed. It yielded hydroxyl numbers between 370 and 420 mg KOH/gsample.

Example 9 Obtaining Polyol Using Routes 2 and 4 (Epoxidation andGlycerolysis} from the Olein Phase of Refined Bleached Deodorized CrudePalm Oil and Using Lead Oxide as Catalyst

200 grams of the olein phase of crude palm oil and 9.97 grams of formicacid were placed in a 500 ml reaction flask, coupled with a refluxcondenser, a heating surface to achieve a temperature of 50° C., andmagnetic agitation to 800 rpm. The reaction was initiated and 22.11grams of hydrogen peroxide were added drop by drop, with constantagitation during 90 minutes. The reaction continued during 2 additionalhours. The reaction of formation of epoxidized oil was evidenced by achange of color from orange to clear yellow.

Hot water washes were then carried out up to a pH close to 5. A wash wasperformed with a of 5% sodium bicarbonate solution and with a 5% sodiumchloride solution. The aqueous phase was discarded through a separatingfunnel and the organic phase was transferred to a lateral releaseErlenmeyer, drying in a vacuum during 3 hours at 80° C. Subsequently theglycerolysis was performed with 100 grams of epoxidized oil, 25.72 gramsof glycerin and 0.3 grams of PbO in a 500 ml reaction flask coupled witha reflux condenser, temperature of 180° C. and agitation at 1300 rpm for45 minutes.

Finally, the polyol obtained was analyzed. It yielded hydroxyl numbersbetween 80 and 90 mg KOH/g sample.

Example 10 Preparation of a Polyurethane Varnish from Polyol Obtained byRoute 1 of the First Method

The pre-polymer was formed taking 30 g of polyol, 76.92 g surfactant and20 ml of MEK (Methyl ethyl ketone) in a 250 ml reaction flask at 50° C.during 30 minutes. The pre-polymer was then transferred to a precipitateflask of 1000 ml and 14.88 grams of TDI (Toluene diisocyanate) wereadded, and stirred mechanically for 3 hours maintaining temperature at70° C. Once the reaction was completed the pre-polymer was cooled to 50°C. and 4.96 grams of MEKO (Methyl ethyl ketoxima) were added to blockthe free NCO groups. This reaction took place during 2 hours. Finally,2.88 grams of TEA (Triethylamine) were added during 30 minutes withvigorous agitation maintaining the temperature at 50° C. An amount of50% w/w of water was then added drop by drop to form an emulsion.

Example 11 Preparation of a Polyurethane Varnish from Polyol Obtained byRoute 1 of the Second Method

The pre-polymer was formed taking 12 g of polyol, 50 g surfactant and 10ml of MEK (methyl ethyl ketone) in a 250 ml reaction flask at 50° C.during 30 minutes. The pre-polymer was then transferred to a precipitateflask of 1000 ml and 12.52 grams of TDI (Toluene diisocyanate) wereadded, and stirred mechanically for 3 hours maintaining temperature at70° C. Once the reaction was completed the pre-polymer was cooled to 50°C. and 5 grams of MEKO (methyl ethyl ketoxima) were added to block thefree NCO groups. This reaction took place during 2 hours. Finally, 2.2grams of TEA (Triethylamine) were added during 30 minutes with vigorousagitation maintaining the temperature at 50° C. An amount of 50% w/w ofwater was then added drop by drop to form an emulsion.

Example 12 Preparation of a Polyurethane Foam from Polyol Obtained byRoute 2

13 g of palm polyol were taken and a mixture 50:50 performed withdiethylene glycol, placed on a heating surface with magnetic agitationto 800 rpm, and then 0.04 g of surfactant, 0.02 g of DBTL (Dibutilindilaurate) as catalyst and 0.2 g of water were added. Finally, 3.8 g ofTDI (Toluene diisocyanate) were added and rapidly stirred manually. Thisreaction this is highly exothermic.

Example 13 Preparation of a Foam of Polyurethane to from of PolyolObtained with the Route 3

10 g of palm polyol were taken and a mixture 50:50 performed withdiethylene glycol, placed on a heating surface with magnetic agitationto 800 rpm, and then 0.27 g of surfactant, 0.19 g of DBTL (Dibutilindilaurate) as catalyst and 2.69 g of water were added. Finally, 13.2 gof TDI (Toluene diisocyanate) were added and rapidly stirred manually.This reaction this is highly exothermic.

Example 14 Preparation of Polyurethane Foam from Polyol Obtained byRoute 4

10 g of palm polyol and 10 g of DEG (diethylene glycol) were weighed,then 0, 19 g of DBTL (Dibutyltin dilaurate) catalyst were added,followed by 2.69 g of water and 0.27 g of surfactant. This premix wasstirred at room temperature for a few minutes and then 13.24 g of MDIwere added. This reaction is highly exothermic.

Example 15 Preparation of a Polyurethane Foam from Polyol Obtained fromExample 6

9 grams of polyol and 1 gram of 1,6 butanediol were premixed andsubmitted to heating in case that the polyol was in a solid state. 0.15grams of silicone 193C and 0.03 grams DBTL (Dibutyltin dilaurate) werethen added and mixed for homogeneity; and finally 1.98 grams of TDI(Toluene diisocyanate) were added and stirred vigorously. The reactionthis is highly exothermic.

Example 16 Preparation of Rigid Polyurethane from Polyol Obtained inExample 7

9 grams of polyol and 1 gram of SDR (Diethylene glycol) are mixed. Themixture, which is solid, is heated. 0.15 grams of silicone 193C and 0.03grams of DBTL (Dibutyltin dilaurate) were added and mixed to achievehomogeneity, and finally 10.5 grams of polymeric MDI (Methylenediisocyanate) are added and stirred vigorously. The reaction is highlyexothermic.

Example 17 Preparation of Rigid Polyurethane from Polyol Obtained inExample 8

9 grams of polyol and 1 gram of SDR (Diethylene glycol) are mixed. Themixture, which is solid, is heated. 0.15 grams of silicone 193C and 0.03grams of DBTL (Dibutyltin dilaurate) were added and mixed to achievehomogeneity, and finally 10.5 grams of polymeric MDI (Methylenediisocyanate) are added and stirred vigorously. The reaction is highlyexothermic.

Example 18 Preparation of Flexible Polyurethane from Polyol Obtained inExample 9

8.5 grams of polyol and 1.5 grams of butanediol are mixed. The mixture,which is solid, is heated. 0.15 grams of silicone 193C, 0.1 grams ofwater, and 0.03 grams of DBTL (Dibutyltin dilaurate) were added andmixed to achieve homogeneity, and finally 4.28 grams of polymeric TDI(toluene diisocyanate) are added and stirred vigorously. The reaction ishighly exothermic.

A feature of polyols and of products obtained from these, in view of theprevious examples, has yielded the following ranges of properties:

Polyols with molecular weights between 314 and 3366 and with a hydroxylnumber between 50 and 450 mgKOH/g sample.

The rigid foams resulting were tested regarding density (according toASTM C373-88) with results between 0.284 and 0.658 g/cm³, Young module(according to ASTM 0695-10) with results between 8.94522 and 54.92330MPa, and maximum effort (according to ASTM 0695-10) with results between0.92037 and 8.29101 MPa.

The semi-rigid foams resulting were tested regarding density (accordingto ASTM C373-88) with results between 0.120 and 0.158 g/cm3, Youngmodule (according to ASTM 0695-10) with results between 0.78727 and1.54311 MPa, and maximum effort (according to ASTM 0695-10) with resultsbetween 0.07012 and 0.09753 MPa.

Example 19 Additional Experimental Runs

Initially we start from the 4 mother routes (Routes 1-4, consideringthat Route 1 comprises Methods I and II). From these routes other routesare derived in the order below:

Mother Derived Route Route 1 1 5 9 13 17 21 25 2 2 6 10 14 18 22 26 3 37 11 15 19 23 27 4 4 8 12 16 20 24 28

In the following table the different experimental runs are summarized,defined by the following parameters:

-   -   Route Number    -   Polyol preparation: reagents        -   operating conditions        -   evaluation results    -   Preparation of polyurethane: reagents        -   operating conditions        -   product characteristics        -   evaluation results

The abbreviation “NA” indicates that the indicated procedure was notcarried out, as it did not become of interest for the inventors.

Preparation of polyol Preparation of Polyurethane Experiment OperationalOperational Evaluation Route No. Reagents conditions Evaluation ResultsReagents conditions Product Features Results 1- 1 Palm OilMaleinisation: T = 0.23 mgKOH/g Prepolymer (polyol), Isocyanatereaction: The varnish is Method 1 maleic anhydride 180° C.; nitrogen t =sample MEKO, TEA, HDI t = 3 h, T = 70° C. separated into two 3 hBlocking with MEKO: phases. Silicone T = 50 C., t = 2 h. varnishNeutralization with intermediately is TEA: T = 50 C., t = observed,appears 30 min, to be in excess. constant stirring. Dark browninitially, but eventually turns light brown. Opaque appearance.Appearance is that of a dispersion (bubbles are observed). 1- 1 Palm Oilt = 30 min. 2 Pre-polymer (polyol) Isocyanate reaction: Method 2 Maleicanhydride Rotoevaporation: T = HDI t = 3 h, T 70° C. Glycerin (99.5% 80°C., 800 rpm, MEKO Blocking with MEKO: purity) vacuum conditions. T = 50C., t = 2 h. Sodium Hydroxide 3. Blocking MEK: T = TEA Neutralizationwith Sodium Chloride 90° c., t = 2 h. 4. TEA: T = 50 C., t = Sulfuricacid (99.5% Blocked 30 min, purity) monoglyceride: T = constantstirring. Methyl ethyl ketone 90° C., t = 3.5 h, 200 rpm. (MEK) 5.Rotoevaporation: Sulfonic Toluene T = 80° C., 800 rpm, Acid vacuumconditions. Toluene 6. Maleinization: T = maleic anhydride 200° C.;nitrogen t = TDI (toluene 3 h. Rotoevaporation: diisocyanate) T = 80°C., 800 rpm, Methyl ethyl vacuum condition, t = ketoxime (MEKO, 1.5 h.99.5% purity). Ethanol 1- 1 Palm Oil Maleinisation: T = Prepolymer(polyol), Isocyanate reaction: It is a viscous Method 1 Maleic anhydride180° C.; nitrogen t = MEKO, TEA, HDI t = 3 h, T = 70° C. mixture inwhich the 3 h Blocking with MEKO: silicone is T = 50 C., t = 2 h.completely Neutralization with separated. Color TEA: T = 50 C., t = darkbrown. 30 min, It contains lots of constant stirring. granules. Freshlyprepared separately is much eventually improves the homogeneity of themixture. 1- 2 Palm Oil Maleinisation: T = 1.32 mgKOH/g NA NA NA NAMethod 1 maleic anhydride 180° C.; nitrogen t = sample 3 h 1- 3 Palm OilMaleinisation: T = 1.43 mgKOH/g NA NA NA NA Method 1 maleic anhydride180° C.; nitrogen t = sample 3 h 1- 1 Palm Oil Maleinisation: T = 2.41mgKOH/g Prepolymer (polyol), Isocyanate reaction: Smooth varnish. Method2 maleic anhydride 180° C.; nitrogen t = sample TDI t = 3 h, T = 70° C.Beige Color. Glycerin (99.5% 3 h MEKO Blocking with MEKO: Mediumviscosity. purity) T = 50 C., t = 2 h. Strong odor. Sodium Hydroxide TEANeutralization with Sodium Chloride TEA: T = 50 C., t = Sulfuric acid(99.5% 30 min, purity) constant stirring. Ethyl methyl ketone (MEK)Sulfonic Acid Toluene Toluene Maleic anhydride Toluene diisocyanate(TDI) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol 1- 2 Palm OilMaleinisation: T = 27.13 mgKOH/g NA NA NA Method 2 Maleic anhydride 180°C.; nitrogen t = sample Glycerin (99.5% 3 h purity) Sodium HydroxideSodium Chloride Sulfuric acid (99.5% purity) Methyl ethyl ketone (MEK)Sulfonic Toluene Acid Toluene maleic anhydride TDI (toluenediisocyanate) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol 1- 3Palm Oil Maleinisation: T = 15.03 mgKOH/g NA NA NA Method 2 Maleicanhydride 180° C.; nitrogen t = sample Glycerin (99.5% 3 h purity)Sodium Hydroxide Sodium Chloride Sulfuric acid (99.5% purity) Methylethyl ketone (MEK) Sulfonic Toluene Acid Toluene maleic anhydride TDI(toluene diisocyanate) Methyl ethyl Ketoxima (MEKO, 99.5% purity).Ethanol 6 1 Palm Oil Glycerolysis: T = 90° C., 19.33 mgKOH/g DiethyleneT, P atmospheric, Yellow. Solid Glycerol t = 2 h. Roto- sample TDIvigorous manual appearance, it Sodium Hydroxide evaporation at lowSurfactant shaking appears greasy. Terbutanol. (20 ml) temperature,Dibutyltin Dilaurate Not observed porous according to the (DBTDL).Hydrochloric Acid volatility of hexane. water n-Hexane. (40 ml) Ddid notform a foam. 6 2 Palm oil Glycerolysis: T = 90° C., polyethylene glycolT, P atmospheric, When reacting Glycerol t = 2 h. Roto- TDI vigorousmanual remained gritty and Sodium hydroxide evaporation at lowSurfactant shaking when put in the soft Terbutanol (20 ml) temperature,Dibutyltin Dilaurate mold it becomes soft according to the (DBTDL) tothe touch, with Hydrochloric Acid volatility of hexane. water time ithardened. n-Hexane. (40 ml) Its color is pale yellow. 20  1 Palm oilMethanolysis: Palm Polyol T, P atmospheric, Porous foam. methanolTemperature: 70° C., diethylene glycol vigorous manual Initially itscolor was Sodium Hydroxide t = 1.5 h, agitation: surfactant shakingwhite, but was Phosphoric acid 1000 rpm. catalyst oxidized and a clear(H3PO4) Rotoevaporation: T = yellow was taken. Hydrogen Peroxide 80° C.,t = 3 h, water It is solid but (H202) vacuum conditions. appears liquidon the benzene Epoxidation: T = 40° C., IPDI surface, seems diethyleneglycol agitation 800 rpm, excess reagent, (DEG) t = 3 h. possibly isFormic acid Rotoevaporation: T = isocyanate. Sodium Chloride 90° C., t =4 h. Feels stiff to the touch. 20  2 Palm oil Methanolysis: Palm PolyolT, P atmospheric vigorous manual It is a color foam. MethanolTemperature: surfactant shaking. White pores was Sodium Hydroxide 70°C., t = 1.5 h, catalyst observed. Phosphoric acid agitation: 1000 rpm.water Wet, it appears a bit (H3P04) Rotoevaporation: T = greasy.Hydrogen peroxide 80° C., t = 3 h, IPDI It is a consistent (H202) vacuumconditions. solid. benzene Epoxidation: T = 40° C. Diethylene glycolAgitation: 800 rpm, (DEG). t = 3 h. formic acid Rotoevaporation: T =Sodium Chloride 90° C., t = 4 h. 2 1 Palm oil. Glycerolysis: T = 90° C.diethylene glycol T, P atmospheric, Orange. Glycerol t = 2 h. Roto- HDIvigorous manual Homogeneous. Sodium Hydroxide evaporation at lowSurfactant shaking. Played more rigid Terbutanol. (20 mi) temperature,Dilaurate dibutyltin than others. according to the (DBTDL) Initially itlooks like a Hydrochloric Acid volatility of hexane. water slurry.n-Hexane. (40 mi) It takes a little time to become solid. 2 2 Palm oilGlycerolysis: T = 90° C., Polyethylleneglycol T, P atmospheric, Themixture is Glycerol t = 2 h. Roto- HDI vigorous manual sandy. Darkyellow. Sodium Hydroxide evaporation at low Surfactant shaking. No foamwas Terbutanol. (20 ml) temperature, Dilaurate dibutyltin formed.according to the (DBTDL) Hydrochloric Acid volatility of hexane. watern-Hexane. (40 ml) 2 3 Palm oil. Glycerolysis: T = 90° C., polyethyleneglycol T, P atmospheric, It was prepared Glycerol t = 2 h. Roto- HDIvigorous manual using an index of sodium hydroxide evaporation at lowSurfactant shaking 0.5. Terbutanol. (20 mi} temperature, Dilauratedibutyltin It is a weak according to the (DBTDL) consistency polymer,Hydrochloric Acid. volatility of hexane. water orange, it breaksn-Hexane. (40 mi) easily. Over time white pieces presented themselvese.2 4 Palm oil. Glycerolysis: T = 90° C., 23.13 mgKOH/g polyethyleneglycol T, P atmospheric, It was prepared Glycerol t = 2 h. Roto- sampleHDI vigorous manual using an index of Sodium Hydroxide evaporation atlow Surfactant shaking 0.8. Tert-butanol (20 ml) temperature, Dilauratedibutyltin It is a product a little according to the (DBTDL) harder thanthe 0.5 Hydrochloric Acid. volatility of hexane water index, however itis n-Hexane. (40 mi) still very fragile. Orange 2 5 Palm oilGlycerolysis: T = 90° C., polyethylene glycol T, P atmospheric, It wasdeveloped Glycerol t = 2 h. Roto- HDI vigorous manual with an indexof 1. Sodium Hydroxide evaporation at low Surfactant shaking Orange, itis a Terbutanol. (20 mi) temperature, Dilaurate dibutyltin product alittle according to the (DBTDL) stronger than the 0.8 Hydrochloric Acid.volatility of hexane water index, however it is n-Hexano. (40 mi) evenmore fragile than expected. 2 6 Palm oil Glycerolysis: T = 90° C.,Polyethyleneglycol T, P atmospheric, Made with an index Glycerol. t = 2h. Roto- HDI vigorous manual of 12. Orange Sodium Hydroxide evaporationat low Surfactant shaking product, stronger Tert-butanol (20 ml)temperature, Dilaurate dibutyltin that lower indices, as according tothe (DBTDL) it consistency is Hydrochloric Acid. volatility of hexanewater harder; however, it is n-Hexane. (40 mi) still brittle and doesnot exhibit the desired rigidity 2 7 Palm oil Glycerolysis: T = 90° C.,523.23 mgKOH/g NA NA NA NA Glycerol. t = 2 h. Roto- sample evaporationat low temperature, according to the volatility of hexane 2 8 Palm oilGlycerolysis: T = Glycerol. 215° C., t = 1 h. Lead Oxide Agitation =1000 rpm. Tert-butanol (20 ml) Roto- Hydrochloric Acid. evaporation at60°, t = n-Hexane. (40 mi) 5 h. 4 1 Palm oil Methanolysis: T: PalmPolyol T, P atmospheric, White color solid Methanol 70° C.m t = 2.5 h.diethylene glycol vigorous manual with good Sodium Hydroxide Agitation1000 rpm. Surfactant shaking homogeneity. Phosphoric acidRotoevaporation: T = Catalyst Observed as (H3PO4) 80° C., t = 3 h.,somewhat greasy. Hydrogen vacuum conditions. Water Liquid on thePeroxide (H2O2) Epoxidation: T = 40° C.: surface. Benzene Agitation: 800rpm, HDI Formic Acid t = 3 h. Sodium Chloride Rotoevaporation: T = 90°C., t = 4 h. 4 2 Palm oil. Methanolysis: T: Palm Polyol T, Patmospheric, Clear yellow color. Methanol 70° C., t = 1.5 h. Diethyleneglycol vigorous manual The mixture Sodium Hydroxide Agitation 1000 rpm.Surfactant shaking exhibited good Phosphoric Acid (H3PO4)Rotoevaporation: T = Catalyst homogeneity. Hydrogen Peroxide 80° C., t =3 h., Water Consistent solid. (H2O2) vacuum conditions. Creamy to thetouch. Benzene Epoxidation: T = HDI Diethylene glycol 40° C., Agitation800 rpm, (DEG). t = 3 h. Formic Acid Rotoevaporation: T) Sodium Chloride90° C., t = 4 h. 4 3 Palm Oil Methanolysis: T: 2.21 mgKOH/g NA NA NAMethanol 70° C., t = 1.5 h. sample Sodium Hydroxide Agitation 1000 rpm.Phosphoric Acid Rotoevaporation: T = (H3PO4) 80° C., t = 3 h., HydrogenPeroxide vacuum conditions. (H2O2) Epoxidation: T = Benzene 40° C.,Agitation 800 rpm, Diethylene glycol t = 3 h. (DEG). Rotoevaporation: T)Formic Acid 90° C., t = 4 h. Sodium Chloride 4 4 Palm Oil Methanolysis:T: NA NA NA Methanol 70° C., t = 1.5 h. Sodium Hydroxide Agitation 1000rpm. Phosphoric Acid Rotoevaporation: T = (H3PO4) 80° C., t = 3 h.,Hydrogen Peroxide vacuum conditions. (H2O2) Epoxidation: T = Benzene 40°C., Agitation 800 rpm, Diethylene glycol t = 3 h. (DEG).Rotoevaporation: T) Formic Acid 90° C., t = 4 h. Sodium Chloride 3 1Palm Oil Reaction with T, P atmospheric, Polymer with a PbOpentaerythritol: T = vigorous manual grasslike and brittlePentaerythritol 200° C., inert shaking consistency. Cream Tert-butanol(20 ml) atmosphere, t = 2 h. colored. Allows mold Hydrochloric Acid.flow. n-Hexane. (40 mi) 3 2 Palm oil Reaction with 11.86 mgKOH/g NA NANA PbO pentaerythritol: T = sample Pentaerythritol 200° C., inertTert-butanol (20 ml) atmosphere, t = 2 h. Hydrochloric Acid. n-Hexane.(40 mi) 3 3 Palm oil Reaction with NA NA NA PbO pentaerythritol: T =Pentaerythritol 200° C., inert Tert-butanol (20 ml) atmosphere, t = 2 h.Hydrochloric Acid. n-Hexane. (40 ml) 5- 1 Palm oil Maleinisation: T0Pre-polymer Reaction with This product did not Method 1 Maleic Anhydride180° C.; Nitrogen MeKO, HDI, TEA isocyanate: t = 3 hr., yield varnish,as it atmosphere, t = 3 h. T = 70° C. MEKO became a solid. Blockage: T =50° C., t = 2 hr. Neutralization with TEA: T = 50° C., t = 30 min.,constant agitation. 5- 1 Palm oil Maleinisation: T = Pre-polymer(polyol) Reaction with This varnish exhibits Method 2 Maleic Anhydride180° C.; Nitrogen MDI isocyanate: t = 3 hr., phase separation. Glycerin(99.5% atmosphere, t = 3 h. Meko T = 70° C. MEKO purity) Blockage: T =50° C., Sodium Hydroxide TEA t = 2 hr. Neutralization Sodium Chloridewith TEA: T = 50° C., Sulfuric Acid (99.5% t = 30 min., constant purity)agitation. Methyl ethyl ketone (MEK) Sulfonic Toluene Acid TolueneMaleic Anhydride Toluene disiocyanate (TDI) Methyl ethyl Ketoxima (MEKO,99.5% purity). Ethanol 7 1 Palm Oil Reaction with Palm Polyol T, Patmospheric, Foam with a greasy PbO pentaerythritol: T = Diethyleneglycol vigorous manual aspect. Very sticky. Pentaerythritol 200° C.,inert Surfactant shaking Yellow color. Difficult Tert-butanol (20 ml)atmosphere, t = 2 h. Catalyst to remove as a Hydrochloric Acid. Waterwhole. n-Hexane. (40 ml) HDI 7 2 Palm oil Reaction with Palm Polyol T, Patmospheric, This product is a PbO pentaerythritol: T = Surfactantvigorous manual modification of the Pentaerythritol 200° C., inertCatalyst shaking route initially Tert-butanol (20 ml) atmosphere, t = 2h. Water planned, because Hydrochloric Acid. the Polyol used ison-Hexane. (40 ml) TDI nly palm oil polyol. Its consistency is a verybrittle foam. Clear yellow color. Does not appear greasy and dries morerapidly thatn the product of this route where the polyol Combined withthe DEG. 8 1 Palm oil Methanolysis: T: Palm Polyol T, P atmospheric, Awhite foam, methanol 70° C., t = 1.5 h. Diethylene glycol vigorousmanual appears somewhat Sodium Hydroxide Agitation 1000 rpm. Surfactantshaking porous. Consistent, Phosphoric acid Rotoevaporation: T =Catalyst but appears brittle. (H3PO4) 80° C., t = 3 h., HydrogenPeroxide vacuum conditions. Water (H202) Epoxidation: T = benzene 40°C., Agitation 800 rpm, MDI diethylene glycol t = 3 h. (DEG)Rotoevaporation: T) Formic acid 90° C., t = 4 h. Sodium Chloride 78  2Palm oil Methanolysis: T: Palm Polyol T, P atmospheric, White colorfoam. Its methanol 70° C., t = 1.5 h. Surfactant vigorous manualappearance is Sodium Hydroxide Agitation 1000 rpm. Catalyst shakingsimilar to gypsum. Phosphoric acid Rotoevaporation: T = Water Verybrittle. (H3PO4) 80° C., t = 3 h., Hydrogen Peroxide vacuum conditions.TDI (H202) Epoxidation: T = benzene 40° C., Agitation 800 rpm,diethylene glycol t = 3 h. (DEG) Rotoevaporation: T) Formic acid 90° C.,t = 4 h. Sodium Chloride 9 1 Palm oil Methanolysis: T: Pre-polymer(polyol) Reaction with Coffee-colored Maleic Anhydride 180° C., MEKO,TEA, TDI isocyanate: varnish. Nitrogen t = 3 hr., T = 70° C. Easilyseparated as atmosphere, t = 3 hr. MEKO Blockage: T = it does not havelow 50° C., t = 2 hr. stability, when left in Neutralization with reposetwo phases TEA: T = 50° C., t = 30 min., are observed and a constantsemisolid layer at agitation. the bottom. Pores observed in itsinterior. 9- 1 Palm Oil Methanolysis: T: Prepolymer (polyol) Reactionwith This product did not Method 2 Maleic anhydride 180° C.,, NitrogenTDI isocyanate: t = 3 hr., yield a varnish, as it Glycerin (99.5%atmosphere, t = 3 hr. Meko T = 70° C. MEKO solidified. purity) Blockage:T = 50° C., Coffee colored solid Sodium Hydroxide TEA t = 2 hr.Neutralization paste. Sodium Chloride with TEA: T = 50° C., Sulfuricacid (99.5% t = 30 min., constant purity) agitation. Methyl ethyl ketone(MEK) Sulfonic Toluene Acid Toluene maleic anhydride TDI (toluenediisocyanate) Methyl ethyl Ketoxima (MEKO, 99.5% purity). Ethanol. 5 1.Polyol of Palm Oil Epoxidation: # OH = 105.52 mg Palm polyol Vigorousagitiation Rapid growth of the crude palm Hydrogen Peroxide Temperature= 50° C. KOH/g sample Diethylene glycol Ambient temperature foam whichsolidified oil using Formic acid Time: 4 hrs. Dibutyltin Dilaureateimmediately. Rigid PbO (DBTDL) foam is not greasy to Sodium BicarnonateAgitation: 800 rpm Silicone 193C the touch. Sodium Chloride GlycerolysisToluene isocyanate (TDI) Glycerin Temp = 215° C. Lead Oxide Time = 45mins. Agitation: 1300 rpm 6 1. Polyol of Crude palm oil Epoxidation: #OH = 202.43 mg Reaction with crude palm Hydrogen Peroxide Temperature =50° C. KOH/g sample continuous bubbling oil using Formic acid Time: 4hrs. and release of heat, PbO Sodium Bicarbonate Agitation: 800 rpmafter a half hour Sodium Chloride Glycerolysis product has not GlycerinTemp = 215° C. solidified, an excess Sodium Hydroxide Time = 45 mins. ofisocyanate is Phosphoric Acid Agitation: 1300 rpm observed. 7 1. Oil RBDPalm Oil Epoxidation: # OH = 418.83 mg Palm Polyol Vigorous agitationSemi-rigid Polyol Hydrogen Peroxide Temperature = 50° C. KOH/g sampleDiethylene glycol Ambient polyurethane, color Of RBD temperatureYellowish, solidified NaOH Formic acid Time: 4 hrs. Dibutyltin Dilauaterapidly. palm. (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) GlycerinTemp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric AcidAgitation: 1300 rpm 8 1. Polyol of RBD Palm Oil Epoxidation: # OH =81.59 mg Palm polyol Vigorous agitation The product has a palm oilHydrogen Peroxide Temperature = 50° C. KOH/g sample Diethylene glycolAmbient grasslike RBD PbO temperature consistence and Formic acid Time:4 hrs. Dibutyltin Dilauate there was no (DBTDL) evience of reaction,Sodium Bicarbonate Agitation: 800 rpm Silicon 193C such as release ofSodium Chloride Glycerolysis Toluene isocyanate heat. (TDI) GlycerinTemp = 215° C. Lead Oxide Time = 45 mins. Agitation: 1300 rpm Combined 1Olein Phase of palm Epoxidation: # OH = 105.52 mg Palm polyol Vigorousagitation The mixture begins 2 and 4 oil KOH/g sample to rise instantlyHydrogen Peroxide Temperature = 50° C. Diethylene glycol Ambient forminga low temperature density foam, it Formic acid Time: 4 hrs. DibutyltinDilauate Evidence of a very (DBTDL) large pore size and SodiumBicarbonate Agitation: 800 rpm Silicone 193C low consistency. SodiumChloride Glycerolysis Toluene isocyanate This product does (TDI) notallow flow, nor Glycerin Temp = 215° C. removal from the Lead Oxide Time= 45 mins. mold. Agitation: 1300 rpm 2 Olein Phase of palm Epoxidation:# OH = 202.43 mg Palm Polyol Vigorous agitation No evidence of oil KOH/gsample reaction, a viscous Hydrogen Peroxide Temperature = 50° C.Dibutyltin Dilauate Ambient yellow liquid pours (DBTDL) temperature whenemptying the Formic acid Time: 4 hrs. Silicon 193C mold. After 1 day itSodium Bicarbonate Agitation: 800 rpm Methylene still has notdiisocyanate (MDI) solidified. Sodium Chloride Glycerolysis WaterGlycerin Temp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric AcidAgitation: 1300 rpm 3 Olein Phase of palm Epoxidation: # OH = 418.83 mgPalm Polyol Vigorous agitation Brittle foam that oil KOH/g sample growsrapidly and Hydrogen Peroxide Temperature = 50° C. Water Ambient whoseinterior is not temperature compact. Formic acid Time: 4 hrs. DibutyltinDilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicon 193CSodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp= 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation:1300 rpm 4 Olein Phase of palm Epoxidation: # OH = 105.52 mg Palm PolyolVigorous agitation No evidence of oil KOH/g sample reaction, emptying ofHydrogen Peroxide Temperature = 50° C. Water Ambient the mold yields atemperature viscous yellowish Formic acid Time: 4 hrs. DibutyltinDilauate creamy liquid. (DBTDL) Sodium Bicarbonate Agitation: 800 rpmSilicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI)Glycerin Temp = 215° C. Lead oxide Time = 45 mins. Agitation: 1300 rpm 5Olein Phase of palm Epoxidation: # OH = 81.59 mg Palm Polyol Vigorousagitation A very compact oil KOH/g sample product was Hydrogen PeroxideTemperature = 50° C. Water Ambient obtained but it is temperature veryfragile to Formic acid Time: 4 hrs. Dibutyltin Dilauate contact. (DBTDL)Sodium Bicarbonate Agitation: 800 rpm Silicon 193C Sodium ChlorideGlycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215° C. Lead oxideTime = 45 mins. Agitation: 1300 rpm 6 Olein Phase of palm Epoxidation: #OH = 202.43 mg Palm Polyol Vigorous agitation Material is rigid to oilKOH/g sample the touch, dries Hydrogen Peroxide Temperature = 50° C.Diethylene glycol Ambient quickly, not greasy, temperature pores aresmaller Formic acid Time: 4 hrs. Dibutyltin Dilauate than for foams(DBTDL) obtained before, Sodium Bicarbonate Agitation: 800 rpm Silicon193C medium density. An Sodium Chloride Glycerolysis Methylene excess ofisocyanate diisocyanate (MDI) is observed. Glycerin Temp = 215° C.Sodium Hydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 7Olein Phase of palm Epoxidation: # OH = 418.83 mg Palm Polyol Vigorousagitation Rigid foam, higher oil KOH/g sample density and smallerHydrogen Peroxide Temperature = 50° C. Diethylene glycol Ambient poresize than the temperature prior one. Color is Formic acid Time: 4 hrs.Dibutyltin Dilauate beige, with a (DBTDL) tendency to light SodiumBicarbonate Agitation: 800 rpm Silicon 193C yellow. Sodium ChlorideGlycerolysis Toluene isocyanate (TDI) Glycerin Temp = 215° C. SodiumHydroxide Time = 45 mins. Phosphoric acid Agitation: 1300 rpm 8 OleinPhase of palm Epoxidation: # OH = 105.52 mg Palm Polyol Vigorousagitation Rigid foam, of oil KOH/g sample greater density and HydrogenPeroxide Temperature = 50° C. Diethylene glycol Ambient lesser pore sizethan temperature the prior one. Color Formic acid Time: 4 hrs.Dibutyltin Dilauate is beige, with (DBTDL) tendency to clear SodiumBicarbonate Agitation: 800 rpm Silicon 193C yellow. Sodium ChlorideGlycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215° C. Leadoxide Time = 45 mins. Agitation: 1300 rpm 9 Olein Phase of palmEpoxidation: # OH = 81.59 mg Palm Polyol Vigorous agitation Rigid foam,medium oil KOH/g sample density and smaller Hydrogen PeroxideTemperature = 50° C. Diethylene glycol Ambient pore size than thetemperature prior one. Color is Formic acid Time: 4 hrs. DibutyltinDilauate beige, with tendency (DBTDL) to clear yellow. SodiumBicarbonate Agitation: 800 rpm Silicon 193C Sodium Chloride GlycerolysisToluene isocyanate (TDI) Glycerin Temp = 215° C. Lead oxide Time = 45mins. Agitation: 1300 rpm 10 Olein Phase of palm Epoxidation: # OH =202.43 mg Palm Polyol Vigorous agitation Rigid sandy oil KOH/g samplepolyurethane, good Hydrogen Temperature = 50° C. 1,6 butanediol Ambientappearance. Peroxide (BDO) temperature Formic acid Time: 4 hrs.Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpmSilicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI)Glycerin Temp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric acidAgitation: 1300 rpm 11 Olein Phase of palm Epoxidation: # OH = 418.83 mgPalm Polyol Vigorous agitation A rigid white oil KOH/g samplepolyurethane was Hydrogen Peroxide Temperature = 50° C. 1,6 butanediolAmbient obtained, very hard. (BDO) temperature Does not permit Formicacid Time: 4 hrs. Dibutyltin Dilauate agitation because (DBTDL) thereaction is very Sodium Bicarbonate Agitation: 800 rpm Silicon 193Cfast. Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) GlycerinTemp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric acidAgitation: 1300 rpm 12 Olein Phase of palm Epoxidation: # OH = 202.43 mgPalm Polyol Vigorous agitation Beige colored oil KOH/g sample polymer,which Hydrogen Peroxide Temperature = 50° C. 1,6 butanediol Ambientexhibited good (BDO) temperature consistency. Formic acid Time: 4 hrs.Dibutyltin Dilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpmSilicon 193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI)Glycerin Temp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric acidAgitation: 1300 rpm 13 Olein Phase of palm Epoxidation: # OH = 418.83 mgPalm Polyol Vigorous agitation A white high density oil KOH/g samplefoam was obtained, Hydrogen Peroxide Temperature = 50° C. 1,6 butanediolAmbient with oval pores, of (BDO) temperature rigid consistence. Formicacid Time: 4 hrs. Dibutyltin Dilauate (DBTDL) Sodium BicarbonateAgitation: 800 rpm Silicon 193C Sodium Chloride Glycerolysis Methylenediisocyanate (MDI) Glycerin Temp = 215° C. Sodium Hydroxide Time = 45mins. Phosphoric acid Agitation: 1300 rpm 14 Olein Phase of palmEpoxidation: # OH = 32.84 mg Palm Polyol Vigorous agitation Manuallyagitated, oil KOH/g sample however no typical Hydrogen PeroxideTemperature = 50° C. Diethylene glycol Ambient features of rectiontemperature were evidenced Formic acid Time: 4 hrs. Dibutyltin Dilauate(temperature (DBTDL) changes, bubbling, Sodium Bicarbonate Agitation:800 rpm Silicone emulsion and growth of foam), Sodium ChlorideGlycerolysis Methylene on the contrary, the diisocyanate liquid aspectstayed. (MDI) Glycerin Temp = 215° C. Sodium Hydroxide Time = 45 mins.Phosphoric acid Agitation: 1300 rpm 15 Olein Phase of palm Epoxidation:# OH = 88.97 mg Palm Polyol Vigorous agitation No formation of foam oilKOH/g sample was witnessed. Hydrogen Peroxide Temperature = 50° C. 1,6butanediol Ambient (BDO) temperature Formic acid Time: 4 hrs. DibutyltinDilauate (DBTDL) Sodium Bicarbonate Agitation: 800 rpm Silicone 193CSodium Chloride Glycerolysis Toluene isocyanate (TDI) Glycerin Temp =215° C. Ethylenediamine Sodium Hydroxide Time = 45 mins. WaterPhosphoric acid Agitation: 1300 rpm 16 Olein Phase of palm Epoxidation:# OH = 88.97 mg Palm Polyol Vigorous agitation Bubbling was oil KOH/gsample observed, as well as Hydrogen Peroxide Temperature = 50° C. 1,6butanediol Ambient an increase in (BDO) temperature temperature and theFormic acid Time: 4 hrs. Dibutyltin Dilauate foam that was seen (DBTDL)solidifying Sodium Bicarbonate Agitation: 800 rpm Silicone 193Ccompletely. Sodium Chloride Glycerolysis Toluene isocyanate (TDI)Glycerin Temp = 215° C. Ethylenediamine Sodium Hydroxide Time = 45 mins.Water Phosphoric Acid Agitation: 1300 rpm 17 Olein Phase of palmEpoxidation: # OH = 401.4 mg Palm polyol Vigorous agitiation Rigidpolyurethane oil KOH/g sample with good Hydrogen Peroxide Temperature =50° C. Diethylene glycol Ambient temperature consistency although Formicacid Time: 3 hrs. Dibutyltin Dilaureate the pore size is big. (DBTDL)Sodium Bicarnonate Agitation: 950 rpm Silicone emulsion Sodium ChlorideGlycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215° C. SodiumHydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 18 OleinPhase of palm Epoxidation: # OH = 401.4 mg Palm polyol Vigorousagitiation Polymer with a small oil KOH/g sample sized pore and goodHydrogen Peroxide Temperature = 50° C. Diethylene glycol Ambienttemperature rigidity properties. Formic acid Time: 3 hrs. DibutyltinDilaureate (DBTDL) Sodium Bicarbonate Agitation: 950 rpm Siliconeemulsion Sodium Chloride Glycerolysis Methylene diisocyanate (MDI)Glycerin Temp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric AcidAgitation: 1300 rpm 19 Olein Phase of palm Epoxidation # OH = 437.56 mgPalm Polyol Vigorous agitation Polymer with a small Young module = oilKOH/g sample pore size and 33.3293 Mpa Hydrogen Peroxide Temperature =50° C. Diethylene glycol Ambient temperature Good properties for MaximumFormic acid Time: 3 hrs. Dibutyltin Dilaureate rigidity. Chosen foreffort = 3.1673 Mpa (DBTDL) the characterizing Sodium BicarnonateAgitation: 950 rpm Silicone emulsion range for rigid PU Sodium ChlorideGlycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215° C. SodiumHydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 20 OleinPhase of palm Epoxidation: # OH = 433.08 mg Palm polyol Vigorousagitiation Presents oil KOH/g sample homogeneity, good Hydrogen PeroxideTemperature = 50° C. Diethylene glycol Ambient temperature pore size,shows Formic acid Time: 3 hrs. Dibutyltin Dilaureate good rigidity.(DBTDL) Sodium Bicarbonate Agitation: 950 rpm Silicone 193C SodiumChloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 215°C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm21 Olein Phase of palm Epoxidation # OH = 263.4 mg Palm Polyol Vigorousagitation Exhibits oil KOH/g sample homogeneity, good Hydrogen PeroxideTemperature = 50° C. Diethylene glycol Ambient temperature pore size andin Formic acid Time: 3 hrs. Dibutyltin Dilaureate general good (DBTDL)physical Sodium Bicarnonate Agitation: 950 rpm Silicone 193C appearance.Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp= 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric Acid Agitation:1300 rpm 22 Olein Phase of palm Epoxidation: # OH = 79.97 mg Palm polyolVigorous agitiation It was found that part oil KOH/g sample of thepolyol did not Hydrogen Peroxide Temperature = 50° C. Diethylene glycolAmbient temperature react and remained Formic acid Time: 3 hrs.Dibutyltin Dilaureate in the lower part, a (DBTDL) white foam beingSodium Bicarbonate Agitation: 950 rpm Silicone emulsion found in theupper Sodium Chloride Glycerolysis Methylene part. The reactiondiisocyanate (MDI) time was slow. Glycerin Temp = 215° C. SodiumHydroxide Time = 45 mins. Phosphoric Acid Agitation: 1300 rpm 23 OleinPhase of palm Epoxidation # OH = 263.4 mg Palm Polyol Vigorous agitationThis polyurethane oil KOH/g sample presents good Hydrogen PeroxideTemperature = 50° C. 1,6 butanediol Ambient temperature features,compared (BDO) with that of the same Formic acid Time: 3 hrs. DibutyltinDilaureate Hydroxil number, (DBTDL) with DEG, however, Sodium Agitation:950 rpm Silicone 193C its rigidity is less. Bicarbonate Sodium ChlorideGlycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 180° C. SodiumHydroxide Time = 25 mins. Phosphoric Acid Agitation: 1300 rpm 24 OleinPhase of palm Epoxidation: # OH = 263.4 mg Palm polyol Vigorousagitiation This polyurethane oil KOH/g sample exhibts good HydrogenPeroxide Temperature = 50° C. Diethylene glycol Ambient temperaturefeatures, it is a semi- Formic acid Time: 3 hrs. Dibutyltin Dilaureaterigid product. (DBTDL) Sodium Bicarbonate Agitation: 950 rpm Silicone193C Sodium Chloride Glycerolysis Methylene diisocyanate (MDI) GlycerinTemp = 180° C. Sodium Hydroxide Time = 25 mins. Phosphoric AcidAgitation: 1300 rpm 25 Olein Phase of palm Epoxidation # OH = 263.4 mgPalm Polyol Vigorous agitation Shows good Density = oil KOH/g samplereplicability and is 0.133 g/cm3 Hydrogen Peroxide Temperature = 50° C.Diethylene glycol Ambient temperature sent for the Formic acid Time: 3hrs. Dibutyltin Dilaureate characterization by (DBTDL) density test.Sodium Bicarnonate Agitation: 950 rpm Silicone 193C Sodium ChlorideGlycerolysis Methylene diisocyanate (MDI) Glycerin Temp = 180° C. SodiumHydroxide Time = 25 mins. Phosphoric Acid Agitation: 1300 rpm 26 OleinPhase of palm Epoxidation: # OH = 263.4 mg Palm polyol Vigorousagitiation Exhibits good Young module = oil KOH/g sample replicabilityand is 1.32276 Mpa Hydrogen Peroxide Temperature = 50° C. Diethyleneglycol Ambient temperature sent for the test by Maximu effort = Formicacid Time: 3 hrs. Dibutyltin Dilaureate characterization of 0.08760 Mpa(DBTDL) compression. Sodium Bicarbonate Agitation: 950 rpm Silicone 193CSodium Chloride Glycerolysis Methylene diisocyanate (MDI) Glycerin Temp= 180° C. Sodium Hydroxide Time = 25 mins. Phosphoric Acid Agitation:1300 rpm 27 Olein Phase of palm Epoxidation # OH = 437.66 mg Palm PolyolVigorous agitation Polymer with a small Density = oil KOH/g sample poresize and good 0.450 g/cm3 Hydrogen Peroxide Temperature = 50° C.Diethylene glycol Ambient temperature velocity features. Formic acidTime: 3 hrs. Dibutyltin Dilaureate Chosen for the rank (DBTDL) of PUSodium Bicarnonate Agitation: 950 rpm Silicone 193C characterization bySodium Chloride Glycerolysis Methylene density. diisocyanate (MDI)Glycerin Temp = 215° C. Sodium Hydroxide Time = 45 mins. Phosphoric AcidAgitation: 1300 rpm

1. A method for the production of polyol from palm oil, characterized bycomprising the following steps: a. mixing palm oil with maleic anhydridein a reactor at a temperature between 170° C. and 190° C. b. heating andagitating the mixture in step a) c. coupling the reactor to a refluxcondenser d. carrying out the reaction under permanent agitation for 3hours
 2. A method for the production of polyol from palm oil,characterized by comprising the following steps: a. mixing, heating andstirring palm oil with sodium hydroxide and a 1:1 solution ofethanol-water b. adding concentrate sulphuric acid to the mixture ofstep a) until the separation of the phases is noted c. adding asaturated solution of sodium chloride to the mixture of step b) d.discarding the aqueous phase obtained in step c), after the completeseparation of the phases e. washing with water at a temperature between70° C. and 80° C. the organic phase left from step d) f. heating andshaking the organic phase of step e) and submitting it to evaporation ina vacuum to obtain the fatty acids g. mixing the fatty acids obtained instep f) with previously blocked glycerol and a catalyst, heating andshaking h. washing with water the mixture of step g) at a temperaturebetween 70° C. and 80° C. i. separating and discard the aqueous phaseobtained in the step h) j. treating the organic phase remaining fromstep i) through evaporation in a vacuum to obtain blocked monoglyceridek. adding maleic anhydride to the blocked monoglyceride from step j),heating and shaking in a low nitrogen atmosphere l. cooling the mixturefrom step k) to 100° C. m. adding sulfuric acid to the product of thereaction in step l) n. wash with water to a temperature between 70° C.and 80° C. and decant the product of the reaction obtained in step m) o.separate the aqueous phase obtained in step m) p. wash the phase organicobtained in step m) q. evaporate the organic phase of step n) to obtainthe polyol
 3. A method in accordance with claim 2 wherein the heatingtemperature in step a) varies between 75° C. and 85° C. and the time ofreaction varies between 28 and 32 minutes.
 4. A method in accordancewith claim 2 wherein the step of washing e) is performed up to the pointwhere the pH is neutral.
 5. A method in accordance with claim 6 whereinthe organic phase of step f) is heated to a temperature between 75° C.and 85° C.
 6. A method in accordance with claim 2, wherein thepreviously blocked glycerol of step g) is obtained through the followingsteps: a. mixing glycerol, MEK (Methyl ethyl ketone), to sulfonictoluene acid as a catalyst and toluene b. heating the mixture of step a)to a temperature between 85 and 95° C. for a time between 110 and 130minutes to obtain blocked glycerol.
 7. A method in accordance with claim2, wherein the mixture of step f) is heated to a temperature between 75°C. and 85° C., for a time between 2 and 3 hours.
 8. A method inaccordance with claim 2, wherein the step of washing h) is is performeduntil the pH is neutral.
 9. A method in accordance with claim 2 whereinthe evaporation of step j) is carried out at a temperature between 85°C. and 95° C. and for a period between 3 and 4 hours.
 10. A method inaccordance with claim 2 wherein the reaction temperature of step k)varies between 190° C. and 210° C. and the time of reaction variesbetween 170 and 190 minutes.
 11. A method in accordance with claim 2wherein the cooling of step l) is carried out until the mixture acquiresa temperature of 100° C., without stop the agitation.
 12. A method inaccordance with claim 6, wherein in step n) the time of reaction variesbetween 50 and 70 minutes.
 13. A method in accordance with claim 6,wherein the evaporation of step q) is carried out at a temperaturebetween 75° C. and 85° C. and for a period of between 1 and 2 hours. 14.A method for the production of polyol to from palm oil, characterized bycomprising the following steps: a. mix palm oil with glycerol,terbutanol as solvent and sodium hydroxide as catalyst in the presenceof heat b. cooling the mixture of step a) c. neutralizing the product ofthe reaction in step a) with hydrochloric acid at 10% d. removing theglycerol and the residual solvent of the mixture in step c) e.submitting the product of step b) to evaporation for removal of solventf) separating the organic phase obtained in step c) by addition ofn-hexane, allowing discarding of the residual glycerin and finallyobtaining polyol
 15. A method in accordance with claims 14, wherein thereaction temperature of step a) varies between 85° C. and 95° C. and thetime of reaction varies between 110 and 130 minutes.
 16. A method inaccordance with claim 14, wherein in step b) the mixture is left to coolto ambient temperature.
 17. A method in accordance with claim 14,wherein the evaporation of step e) is carried out at a temperaturebetween 85° C. and 95° C. and for a period between 2 and 3 hours.
 18. Amethod for the production of polyol from palm oil, characterized bycomprising the following steps: a. Mixing palm oil, pentaerythritol andlead oxide, in the presence of heat, agitation and an inert nitrogenatmosphere. b. cooling the mixture of step a) c. treating mixture ofstep b) with n-hexane, allowing the formation of two phases, stirringand releasing the pressure. d. discarding the precipitate obtained instep c) which contains glycerol e. submitting the organic phase toevaporation for obtaining the polyol
 19. A method in accordance withclaim 18, wherein the reaction temperature of step a) varies between195° C. and 205° C., and the time of reaction varies between 110 and 130minutes.
 20. A method in accordance with claim 18, wherein in step b)the mixture is left to cool to ambient temperature.
 21. A method inaccordance with claim 18, wherein the evaporation of step e) is carriedout at a temperature between 65° C. and 75° C. and during a periodbetween 2 and 3 hours.
 22. Method for the production of polyol from palmoil, characterized by comprising the following steps: a. producing fattyacid methyl esters (FAME) from the following steps: mix palm oil,methanol and sodium hydroxide at a temperature between 65° C. and 75° C.and agitate during a period between 1 and 2 hours discard the glycerinphase that is at the bottom after the previous reaction wash the phaseof interest obtained in the first step with 0.015N phosphoric acid at atemperature between 55° C. and 65° C. discard solids formed wash theproduct obtained in the previous step with water at a temperaturebetween 55° C. and 65° C. until the pH this is neutral evaporate theproduct of the previous step (FAME) to remove excess methanol at atemperature between 75° C. and 85° C. and during period between 2 and 3hours. b. mix FAME obtained in step a) with formic acid in the presenceof hydrogen peroxide c. wash the product obtained in step b) with waterat a temperature between 50° C. and 60° C. d. wash the product obtainedin step c) with sodium bicarbonate at 5% e. wash the product obtained instep d) with sodium chloride at 5% f. wash the product obtained in stepe) with water at a temperature between 50° C. and 60° C. g. evaporatethe solution obtained in step c) to remove the moisture allowingobtaining the polyol
 23. A method in accordance with claim 22, whereinthe reaction temperature in step b) varies between 40° C. and 50° C. andthe time of reaction varies between 10 and 11 hours, after of theaddition of hydrogen peroxide.
 24. A method in accordance with claim 22,wherein the washing step c) is performed until the pH of the solution is5.
 25. A method in accordance with claim 22, wherein the washing in stepf) is performed until the pH is neutral.
 26. A method in accordance withclaim 30, wherein the evaporation of step g) is carried out at atemperature between 70° C. and 90° C. and for a period between 3 and 4hours.
 27. A method for the production of polyol from palm oil,characterized by comprising the following steps: a. mix a source of palmoil with formic acid, in the presence of heat b. add hydrogen peroxideto the mixture of step a) and shake c. wash the reaction product of stepb) with water, at a temperature between 55° C. and 65 ° C. d. wash theproduct obtained in the step c) with sodium bicarbonate at 5% e. washthe product of reaction of step d) with water, at a temperature between55° C. and 65° C. f. wash the product obtained in step e) with sodiumchloride at 5% g. discard the phase aqueous obtained in step f) h. dryto the empty the phase organic remaining of step f) i. mix theepoxidized oil obtained in step g) with glycerol and catalyst, in thepresence of heat and agitation
 28. A method in accordance with claim 27,wherein the source of palm oil in step a) is the olein phase of crudepalm oils.
 29. A method in accordance with claim 27, wherein the sourceof palm oil in step a) is the olein phase of refined bleached anddeodorized palm oil (RBD).
 30. A method in accordance with claim 27,wherein the catalyst of step h) is lead oxide.
 31. A method inaccordance with claim 27, wherein the catalyst of step h) is sodiumhydroxide.
 32. A method in accordance with claim 27, wherein the washingof step c) is performed until the pH of the solution is
 5. 33. A methodin accordance with claim 27, wherein the reaction temperature of step b)varies between 45° C. and 55° C. and the time of reaction varies between1 and 2 hours after of the addition of hydrogen peroxide.
 34. A methodin accordance with claim 27, wherein the reaction temperature of step i)varies between 170° C. and 190° C. and the time of reaction variesbetween 40 and 50 minutes.
 35. A polyol characterized by having amolecular weight between 374 and 3366 and 374, with a hydroxyl numberbetween 50 and 450 mgKOH/g sample.
 36. A rigid polyurethane foamcharacterized by having a density between 0.284 g/cm³ and 0.658 g/cm³ ,Young module between 8.94522 MPa and 54.92330 MPa and maximum effortbetween 0.92037 MPa and 8.29101 MPa.
 37. Semirigid polyurethane foamcharacterized by having a density between 0.120 g/cm³ and 0.158 g/cm³,Young modulo between 0.78727 MPa and 1.54311 MPa, and maximum effortbetween 0.07012 MPa and 0.09753 MPa.